Aniline → N,9-Diphenyl-9H-carbazol-3-amine

HRID 1993085Notes

Reaction equation

HRID 1993085 reaction equation
C1(C)C(C)=CC=CC=1.[NH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.Br[C:17]1[CH:18]=[CH:19][C:20]2[N:21]([C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[C:22]3[C:27]([C:28]=2[CH:29]=1)=[CH:26][CH:25]=[CH:24][CH:23]=3.CC(C)([O-])C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[Fe+2].C1(C)C=CC=CC=1>[C:10]1([NH:9][C:25]2[CH:24]=[CH:23][C:22]3[N:21]([C:30]4[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=4)[C:20]4[C:28]([C:27]=3[CH:26]=2)=[CH:29][CH:17]=[CH:18][CH:19]=4)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

8

Reactant 4

HCID 6115AnilineHCID 7237O-XyleneHCID 189426243-Bromo-9-phenylcarbazoleHCID 23676156Sodium t-butoxide

Product 1

HCID 59815954N,9-Diphenyl-9H-carbazol-3-amineYield 75%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 152416121,1`-Bis(diphenylphosphino)ferroceneCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

Under a nitrogen atmosphere, 110 mL of dehydrated xylene and 7.0 g (75 mmol) of aniline were added to a mixture of 19 g (60 mmol) of 3-bromo-9-phenylcarbazole, 340 mg (0.6 mmol) of bis(dibenzylideneacetone)palladium (0), 1.6 g (3.0 mmol) of 1,1-bis(diphenylphosphino)ferrocene, and 13 g (180 mmol) of sodium-tert-butoxide. This mixture was stirred under a nitrogen atmosphere for 7.5 hours while heating at 90° C. After the termination of the reaction, about 500 mL of hot toluene was added to the suspension and this suspension was filtered through florisil, alumina, and Celite®. The obtained filtrate was concentrated, and its residue is mixed with hexane-ethyl acetate and irradiated with an ultrasonic wave. The obtained suspension was filtered and the residue was dried to obtain 15 g (yield: 75%) of 3-(N-phenylamino)-9-phenylcarbazole which was cream-colored powder. NMR data are shown below. 1H-NMR (300 MHz, CDCl3): δ=6.84 (t, J=6.9, 1H), 6.97 (d, J=7.8, 2H), 7.20-7.61 (m, 13H), 7.90 (s, 1H), 8.04 (d, J=7.8, 1H). A 1H-NMR chart is shown in FIG. 25, and an enlarged view of a portion of 5.0 ppm to 9.0 ppm in FIG. 25 is shown in FIG. 26.

Workup

  1. additionwas added to the suspension
  2. filtrationthis suspension was filtered through florisil, alumina, and Celite®
  3. concentrationThe obtained filtrate was concentrated
  4. additionits residue is mixed with hexane-ethyl acetate
  5. customirradiated with an ultrasonic wave
  6. filtrationThe obtained suspension was filtered
  7. customthe residue was dried

Sources & evidence

ORD record
ord-4587c9069b7f44e49c645ecb1a7c1a1e
Source dataset
uspto-grants-2010_01
Patent number
US07649197B2

Reaction notes

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